DIACRYLATES ET ACRYLATES SUBSTITUES DE TETRABROMOXYLYLENE

TETRABROMOXYLYLENE DIACRYLATES AND SUBSTITUTED ACRYLATES

Abrégé anglais

ABSTRACT OF THE DISCLOSURE:
Tetrahaloxylylene diesters having the general formulae:
<IMG> (I)
<IMG> (II)
wherein R represents hydrogen or a methyl group and X is bromine
or chlorine, with the proviso that, when X is chlorine, there is
no more than one chlorine atom per molecule, are obtained by
converting acrylic acid or methacrylic acid in a polar solvent
into an alkali salt thereof, and reacting m- or o- tetrabromo-
xylylene dichloride with a stoichiometric excess of from 1 to
10 mole % of the alkali salt obtained, in the presence of a
polymerisation inhibitor at 50 to 150°C. These diesters are
particularly useful as reactive crosslinkers for unsaturated
compounds and fire-retarding additives to polymers.

Revendications

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. A process for the preparation of tetrahaloxylylene
diesters having the general formulae:
<IMG> (I)
(II)
<IMG>
wherein R represents hydrogen or a methyl group and X is bromine
or chlorine, with the proviso that, when X is chlorine, there is
no more than one chlorine atom per molecule, which process
comprises converting acrylic acid or methacrylic acid in a
polar solvent into an alkali salt thereof, and reacting m- or o-
tetrabromoxylylene dichloride with a stoichiometric excess of
from 1 to 10 mole % of the alkali salt obtained, in the presence
of a polymerisation inhibitor at 50 to 150°C to form the desired
ester of the formulae (I) or (II)
2. Process according to claim 1, wherein the polar
solvent is selected from the group comprising C1 to C4-alcohols,
ether alcohols, glycols, tetrahydrofuran, dimethoxyethane, dioxane,
dimethylformamide, dimethylacetamide, methyl pyrrolido and

dimethyl sulphoxide.
3. Process according to claim 2, wherein the polar
solvent is ethylene glycol monoethyl ether.
4. Process according to claim 1, wherein the poly-
merisation inhibitor is selected from the group comprising
hydroquinone, p-benzoquinone, pyrocatechol, 4-tert.butyl pyro-
cathecol, hydroquinone monoethyl ether and 2,4,6-tri-tert.butyl
phenol.
5. Process according to claim 4, wherein the poly-
merisation inhibitor is hydroquinone.
6. Process according to claim 1, wherein the salt
formation is effected by reaction of the acrylic or methacrylic
acid with an alkali compound selected from the group comprising
alkali carbonates, alkali bicarbonates, alkali hydroxides and
tertiary amines, the acid being used in a slight stoichiometric
excess relative to the alkali compound.
7. Process according to claim 1, wherein the reaction
between the m- or o- tetrabromoxylylene dichloride and the alkali
salt is effected at a temperature of from 80 to 130°C.
8. Tetrahaloxylylene diesters having the general
formulae:

<IMG> (I)
<IMG> (II)
wherein R represents hydrogen or a methyl group and X is bromine
or chlorine, with the proviso that, when X is chlorine, there
is no more than one chlorine atom per molecule.
9. A diester according to claim 8, characterised in
that it is tetrabromo-m-xylylene-bis-methacrylate.
10. A diester according to claim 8, characterised in
that it is tetrabromo-m-xylylene-bis-acrylate.
11. A diester according to claim 8, characterised in
that it is tetrabromo-o-xylylene-bis-methacrylate.
12. A diester according to claim 8, characterised in
that it is tetrabromo-o-xylylene-bis-acrylate.

Description

G~rmall Offenlegun~sscl~rift No. 2,508,468 in the name of
~pplicants, published on September 9, 1976, describes inter alia
tetrabromo-p-xylylene diacrylate and dimethacrylate, and a
process for their production.
It has now been proved possible to produce tetra-
bromo-_-xylylene diacrylate and dimethacrylate as well as
tetrabromo-_-xylylene diacrylate and dimethacrylate.
The unsaturated esters are produced by reacting the
meta- or ortho-isomers of tetrabromoxylylene dichloride with
the alkali salts of ~meth)acrylic acid in polar solvents miscible
with water to a small extent at least.
The present invention thus relates to tetrahaloxylylene
diesters having the general formulae:
o
R O ~ CH2-O-C-C=CH2 ~I)
I ll / R
:'. H2C=C-C-O-CH2 X
X X
X ~ X (II)
R R R lR
H2C=C-C-O-CH2 CH2--0-C-C=CH2
:
in which R represents hydrogen or a methyl group and X is bromine
or chlorine, with the proviso that, when X is chlorine, there is
no more than one chlorine atom per molecule.
The invention also relates to a process for the
production of the compounds having the above formulae (I) and
(II) which is characterized in that acrylic acid or methacrylic acid
is converted in a polar solvent into an alkali salt thereof,
- 1 -

1080ZSO
after which m- or Q-tetrsbromoxylylene dichloride i3 re~cted
with a stoichiometric excess of from 1 to 10 mole % of the alkali
salt of the acid in the pre~ence of a polymerisation inhibitor
at 50 to 150C to form the de~ired ester of the formulae (I) or
(II).
The starting msterials can be obtained by brominating
the nucleus and chlorinating the side chain of m- and o-xylllane
or mixture~ thereo~.
; A~ a rule, the compound~ obt~ined in this way contsin
bromine as the sole nuclear substituent, although in some cases
some of the bromine bonded to the aromatic nucleu~ is replaced
by chlorine which fsct is taken into account by the use of the
substituent X. ~n general, the quantity of chlorine amounts to
no more than 1 Cl per molecule, 80 that m- or o-xylylene bi~-
e~ters with the summation formula
o
$~; C6Br4.0 to 3 oClo to 1 o(CH2-0-C-C-CH2)2
I R
are obtsined as end product and may be used in the same way.
The new compounds are obtained by reaction with tmeth)
acrylic acid.
~he unsaturated carboxylic acids are converted into the
alkaii salts in a polar organic ~olvent by the addition of,
for example, alkali c~rbonstes or bicarbonates o~ alkali
, .
~; hydroxide~ or tertiary smines, ~uch as triethyl or tributyl-
i~ amine. Among the alkali compounds, the carbonates and hydroxides
are greatly preferred, although it is also pos~lble to use the
bicarbonates or, in some cases, thè alkali alcoholates, above all
the methylate~. Tetrabromoxylylene dichloride is then added to
a s~oichiometric excess of from 1 to 10 mole % of the alkali
salt of the unsaturated carboxylic acid snd reacted in the usual
-2-
'

l~Of~SO
way in the presence of a polymerisation inhibitor at 50 to 150C
to form the ester.
The ~alt formatlon between (meth)acrylic acid and
alkali carbonate or alkall hydroxide generslly take~ place at
temperatures in the rsnge from 10 to 80C, preferably at room
temperature, the alkali carbonate being added to the acid
initially introduced in the ~olvent in portion~ with ~tirring
following addition of the polymeri~ation inhibitor, in order to
avoir exce~ive foaming (evolution of C02) In cases where
alkali hydroxide is used, it is preferably added in the form of
a concentrated aqueou~ solution. A~ter the tetrabromoxylylene
dichloride ha~ been introduc~d, the reaction mixture i~ heated
to the resction temperature in the range from 50 to 150C,
prefersbly in the range from 80 to 130C, snd left to react until
an almost complete conversion is obtained. The reaction time
varie~ from 0.5 to 5 hours, The reaction may be followed by
~uantitatively determining the alkali chloride formed, for
example by Mohr~s chloride determination.
Examples of suitable polar sol~ent~ sre C1 to C4
alcohols, giycols, ether alcohols, tetrahydrofuran, dioxane,
dimethoxyethane, dimethylformamide, dimethylacetsmide, N-methyl
pyrrolidone and dimethyl sulphoxide It i9 preferred to use
ethylene glycol monomethyl ether.
Suitable inhibitors are hydroquinone, p-benzoquinone,
pyrocatechol, 4-tert.-butyl pyrocatechol, hydroquinone monomethyl
ether, 2,4,6-tri-tert.-butyl phenol. It i9 preferred to use
hydroquinone. Na2C03 or K2C03 is preferably used a~ the alkali
carbonate, whilst NaOH or KOH is preferably used as the alkali
hydroxide.
The stoichiometric exces~ of from 1 to 10 mole % of the
alkali salt of the acid relative to the tetrabromoxylylene
,,
dichloride is intended to guarantee a complete conver~ion of

l~V2~0
the last of the above-mentioned starting compound~. ~he exces~
quantities of alkali (meth)acrylate may readily be ~epar~ted
off together with the alkali chloride formed when the re~ction
mixture i ~ worke d up .
Alkali carbonate or alkali hydroxide and unsaturated
acidqimay be u~ed in equlvalent quantities However, it has
proved to be of sdvantage, in order to avoid the formation of
undesirable secondary products, such as adducts of the ethylene
glycol monomethyl ether used as sQlvent with the C=C-double
bond of the (meth3acrylic acid, or polymer~ actually formed
during the esterification reaction by vinyl polymerisation,
to use the un~aturated acid in a ~light stoichiometric excess
relative to the alkali carbonates used for salt formation, 90
that the reaction mixture shows &n acid reaction both during
and after salt formation. In this way, the alkali-catalysed
addition of methyl glycol to the acid double bond is prevented
~nd the phenolic inhibitor adequately develops its effect.
On completion of the reaction, all the reaction
products are in ~olution, except for the alkali chloride and
small already polymerised or cros~linked quantities of the (meth)
acrylic ester. The undissolved products can be separated off by
filtration or centrifuging. When the filtrate is cooled, the
esters of formulae (I) and (II) generally crystallise out in
high yield~ and adequate purity. They are ~eparated off, washed
with water until free from chloride and preferably dried a~
room temperature. In order to isolate the esters, the reaction
solution may also be poured in water, optionslly after the
fraction~ undi~solved under heat have been separated off, and
the reaction products precipitated in thi~ way. It may be
advisable to adopt this procedure in the case of tetrabromoxyly-
lene dimethacrylate which crystallises out somewhat more sluggish-
ly.
--4--

~v~o
Tllc ~Insclturated es~el-7 o~ ormulae (I) and (II)
according to the invention may be used as reactive crosslinkers for
unsaturated c~mpounds.
The new compounds thus obtained are crystalline
compounds characterized by their melting points.
The esters according to the invention may be used as
~; reactive crosslinkers for unsaturated compounds. They have
valuable properties as fire-retarding additives to polymers,
~;~ for which purpose they may be used either as such or preferablyin the form of polymers or copolymers. In addition to their
excellent flameproofing effect, the polymers and copolymers
are distinguished by particularly firm anchorage in the polymers,
which is obviously attributable to polar molecule fractions and
, also to angling of the polymers and copolymers through the _-
and m-position of the chain-linking organic substituents.
Preferred embodiments of the invention will now be
better understood with reference to the following non restrictive
examples.
, _XAMPLE 1
In a three-necked flask equipped with a stirrer and
reflux condenser, 18.08 g (0.21 mole) of methacrylic acid and
0.8 g of hydroquinone as polymerisation inhibitor are dissolved
in 200 ml of methyl glycol and 8 g (0.2 mole) of sodium hydroxide,
dissolved in 8 g of water, added all at once to the resulting
solution with stirring. Following the addition of 49.1 g (0.1
, mole) of tetrabromo-m-xylylene dichloride, the contents of the
flask are heated to 110C and left to react for 1 hour at 110C.
Determination with chloride according to Mohr showed a 93~
conversion. After another 30 minutes at 110C, some small
undissolved fractions are separated off by filtration while still
hot, and the reaction solution left to cool.
.
-- 5 --

lVt~V;~O
A white cry~talline deposit is precipltated. It is
filtered under ~uction, washed once with methyl glycol and then
repe~tedly with water,
The reaction product wa~ dried in vacuo at room
temperature over P205 until con~tant in weight.
The yield amounted to 46 g of tetrabromo-m-xylylene-
bi~-methacrylate, which corre~pond~ to 79.9~ o~ the theoreti¢al.
l~ Melting point M.p, = 98 - 99C, Determination of the double
bond content in accordance with Beesing's method re~ealed a
purity of the bis-methacrylate of 97.2%.
EXAMP~E 2
.
11.3 g of anhydrou~ soda are added in portlons with
I . ,
~/ stirring over a period of 30 minute~ at room temperature to a
solution of 15.2 g of acrylic acid and 1.4 g of hydroquinone in
1 180 ml of methyl glycol.
49.1 g of tetrabromo-m-xylylene dichloride are then
added, followed by hesting for 2.5 h to a temperature of 110C.
The reaction mixture i~ filtered while still hot and
then left to cool in an ice bath.
The crystalline deposit is filtered under suction,
wa~hed once with cold methyl glycol and then repeatedly with
water. It is dried in vacuo, at room temperature over P205 until
constant in weight.
; Tetrabromo-m-xylgl~Y~bi~-acrylate is obtained in a
yield of 42.3 g, corresponding to 75,5% of the theoretical.
Melting point M,p. = 105 - 108C,
7 EXAMPIæ 3
8 g (0.2 mole) of sodium hydroxide in ~olid form
(tablet~) are ~dded wlth stirring to 8 solution of 18.08 g
(0.21 mole) of methacrylic acid and 1.2 g of hydroquinone in 200
ml Qf methyl glycol. The NaOH di~solves in 1.5 h at room
temperature, sccompanied by salt formation. 49.1 g (0.1 mole) of
,
: -6- .

8~ 2 ~0
tetrabromo-o-xylylene dichloride are added and th~ reaction
mixture i9 heated to 110C. After 1 5 h ~t 110C, the reaction
is termlnated, the reaction mixture filtered while ~till hot
and the filtrate cooled in an ice bath. The cry~tal sludge i9
filtered under 3uction, wa~hed once with methyl elycol snd then
repeatedly with water (until the filtrate i~ free from Cl ).
After drying to constancy of weight, tetrabromo-o-
~ylylene-bi~-methacrylate i~ obtained in a yield of 38.6 g,
corresponding to 67% of the theoretical. Melting point M.p. =
64 - 66C. Double bond content according to Beesing: 98.1~.
EXAMPIæ 4
~ ollowing the procedure of Example 3, 34.4 g (61% of
the theoretical) of tetrabromo-o-~ylylene-bis-acrylate are
obtained after 8 reaction time of 2 hours at 110C from the
following reaction components: 15.2 g of acrylic acid, 8 g of
NaOH as salt former in the form of a 50~o aqueous solution, 1.2 g
of hydroq~inone as polymerisation inhibitor, 49.2 g of tetra-
bromo-o-xylylene dichloride and 200 ml of methyl glycol as
solvent. Melting point M p = 100 - 103C.
A p~le yellow, highly viscous oil can be isolated from
the mother liquor by the addition of water (600 ml). When
sub~equently dried~ thi~ oil hardens into a horn-like mass
Yield: 14.3 g, corre~ponding to 25.5% of the theoretical.
Melting range: 92 - 99C Double bond content according to
Bee~ing 91.7%.
'''
,,
--7--